The polyamine



United States Patent M 3,127,354 PROCESS FOR INHIBITIN G FOAM EMPLOYING METHYLOL PHENOL DERIVATIVES Melvin De Groote, St. Louis, and Kwan-ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, a corporation of Delaware No Drawing. Original application May 12, 1960, Ser. No. 28,514. Divided and this application Apr. 10, 1961, Ser. No. 101,626

12 Claims. (Cl. 252-321) This application is a division of our copending application Serial No. 28,514, filed May 12, 1960, which latter application is a continuation-in-part of our copending application Serial No. 730,510, filed April 24, 1958, now abandoned. See also our copending application Serial No. 799,488, filed March 16, 1959, now abandoned, which is a division of Serial No. 730,510. This invention relates to a process for inhibiting foam employing (1) oxyalkylated, (2) acylated, (3) oxyalkylated then acylated, (4) acylated then oxyalkylated, and (5 acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols. These substituted phenols are produced by a process which is characterized by reacting a preformed methylol phenol (i.e., formed prior to the addition of the polyamine) with at least one mole of a secondary polyamine per equivalent of methylol group on the phenol, in the absence of an extraneous catalyst (in the case of an aqueous reaction mixture, the pH of the reaction mixture being determined solely by the methylol phenol and the secondary polyamine), until about one mole of water per equivalent of methylol group is removed; and then reacting this product with (1) an oxyalkylating agent, (2) an acylating agent, (3) an oxyalkylating agent then an acylating agent, (4) an acylating agent then an oxyalkylating agent or (5) an acylating agent then an oxyalkylating agent and then an acylating agent.

The reasons for the unexpected monomeric form and properties of the polyaminomethyl phenol are not understood. However, we have discovered that when (1) A preformed methylolphenol (i.e., formed prior to the addition of the polyamine) employed as a starting material is reacted with (2) A polyamine which contains at least one secondary amino group (3) In amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol,

(4) In the absence of an extraneous catalyst, until (5) About one mole of water per equivalent of methylol group is removed, then a monomeric polyaminomethyl phenol is produced which is capable of being oxyalklated, acylated, oxyalkylated then aeylated, or acylated then oxyalkylated, or acylated, then oxyalkylated and then acylated to provide the superior products employed in the processes of this invention. All of the above five conditions are critical for the production of these monomeric polyaminomethyl phenols.

In contrast, if the methylol phenol is not preformed but is formed in the presence of the polyamine, or the preformed methylol phenol is condensed with the polyamine in the presence of an extraneous catalyst, either acidic or basic, for example, basic or alkaline materials 3,127,354 Patented Mar. 31, 1964 such as NaOH, Ca(OH) Na CO sodium methylate, etc., a polymeric product is formed. Thus, if an alkali metal phenate is employed in place of the free phenol, or even if a lesser quantity of alkali metal is present than is required to form the phenate, a polymeric product is formed. Where a polyamine containing only primary amino groups and no secondary amino groups is reacted with a methylol phenol, a polymeric product is also produced. Similarly, where less than one mole of secondary amine is reacted per equivalent of methylol group, a polymeric product is also formed.

In general, the monomeric polyaminomethyl phenols are prepared by condensing the methylol phenol with the secondary amine as disclosed above, said condensation being conducted at a temperature sufiiciently high to eliminate water but below the pyrolytic point of the reactants and product, for example, at to 200 C., but preferably at to C. During the course of the condensation water can be removed by any suitable means, for example, by use of an azeotroping agent, reduced pressure, combinations thereof, etc. Measuring the Water given oif during the reaction is a convenient method of judging completion of the reaction.

The classes of methylol phenols employed in the condensation are as follows: I M0nophenols.-A phenol containing 1, 2 or 3 methylol groups in the ortho or para position (i.e., the 2, 4, 6 positions), the remaining positions on the ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, and alkoxy, etc., groups, and having but one nuclear linked hydroxyl group.

Diphenols.0ne type is a diphenol containing two hydroxybenzene radicals directly joined together through the ortho or para (i.e., 2, 4, or 6) position with a bond joining the carbon of one ring with the carbon of the other ring, each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.

A second type is a diphenol containing two hydroxybenzene radicals joined together through the ortho or para (i.e., 2, 4, or 6 position) with a bridge joining the carbon of one ring to a carbon of the other ring, said bridge being, for example, alkylene, alkylidene, oxygen, carbonyl, sulfur, sulfoxide and sulfone, etc., each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyamino-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.

The secondary polyaun-ines employed in producing the condensate are illustrated by the following general formula:

R HN/ where at least one of the Rs contains an amino group and the Rs contain alkyl, alkoxy, rcycloalkyl, aryl, aralkyl, alkaryl radicals, and the corresponding radicals containing heterocyclic radicals, hydroxy radicals, etc. The Rs may also be joined together to form heterocyclic polyamines. The preferred classes of polyamines are the alkylene polyamines, the hydroxylated alkylene polyamines, branched polyamines containing at least three primary amino groups, and polyamines containing cyclic amidine groups. The only limitation is that there shall be present in the polyamine at least one secondary amino group which is not bonded directly to a negative radical which reduces the basicity of the amine, such as a phenyl group.

An unusual feature of the products employed in the processes of the present invention is the discovery that methylol phenols react more readily under the herein specified conditions with secondary amino groups than with primary amino groups. Thus, where both primary and secondary amino groups are present in the same molecule, reaction occurs more readily with the secondary amino group. However, where the polyamine contains only primary amino groups, the product formed under reaction conditions as mentioned above is an insoluble In contrast, where the same number of primary amino groups are present on the amine in addition to at least one secondary amino group, reaction occurs predominantly wi-Lh the secondary amino group to form nonresinous derivatives. Thus, where trimethylol phenol is reacted with ethylene diamine, an insoluble resinous composition is produced. However, Where diethylene triamine, a compound having just as many primary amino groups as ethylene diamine, is reacted, according to this invention a non-resinous product is unexpectedly formed.

The term monomeric as employed in the specification and claims refers to a polyaminomethylphenol containing within the molecular unit one aromatic unit corresponding to the aromatic unit derived from the starting methylol phenol and one polyamine unit cEor each methylol group originally in the phenol. This is in contrast to a polymeric or resinous polyaminomethyl phenol containing within the molecular unit more than one aromatic unit and/or more than one polyamino unit for each methylol group.

The monomeric products produced by the condensation of the methylol phenol and the secondary amine may be illustrated by the following idealized formula:

where A is the aromatic unit corresponding to that of the methylol reactant, and the remainder of the molecule is the polyaminomethyl radical, one for each of the original methylol groups.

'Ihis condensation reaction may be followed by oxyalkylation in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglyoide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions or propylene oxide and ethylene oxide, or smaller proportions thereof in relation to the methylol phenol-amine condensation product. Thus, the molar ratio of alkylene oxide to amine condensate can range within wide limits, for example, from a 1:1 mole ratio to a ratio of 100021, or higher, but preferably 1 to 200. By proper control,

desired hydrophilic or hydrophobic properties are impatted to the composition. As is well known, oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from -200 C., and pressures of from 10 to 200 p.s.i., and times of from 15 min. to several days. Preferably oxyalkylation reactions are carried out at 80 to C. and 10 to 30 psi For conditions of oxyalkylation reactions see US. Patent 2,792,369 and other patents mentioned therein.

As in the amine condensation, acylation is conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from to 280 C., but preferably at 140 to 200 C. in acylating, one should control the reaction so that the phenolic hydroxyls are not acylated. Because acyl halides and :anhydrides are capable of reacting with phenolic hydroxyls, this type of acylation should be avoided. It should be realized that either oxyalkylation or acylation can be employed alone or each alternately, either one preceding the other. In addition, the amine condensate can be acylated, then oxyalkylated and then reacylated. The amount of acylation agent reacted will depend on reactive groups or the compounds and properties desired in the final product, for example, the molar ratios of acylation agent to amine condensate can range from 1 to 15, or higher, but preferably 1 to 4.

Where the above amine condensates are treated with alkylene oxides, the product formed will depend on many factors, for example, Whether the amine employed is hydroxylated, etc. Where the amines employed are nonhydroxylated, the amine condensate is at least susceptible to oxyalkylation through the phenolic hydroxyl radical. Although the polyamine is non-hydroxylated, it may have one or more primary or secondary amino groups which may be oxyalkylated, for example, in the case of tetraethylene pentamine. Such groups may or may not be susceptible to oxyalkylation for reasons which are obscure. Where the non-hydroxylated amine contains a plurality of secondary amino groups, wherein one or more is susceptible to oxyalkylation, or primary amino groups, oxya-lkylation may occur in those positions. Thus, in the case of the non-hydroxylated polyamines oxyalkylation may take place not only at the phenolic hydroxyl group but also at one or more of the available amino groups. Where the amine condensate is hydroxyalklated, this latter group furnishes an additional position of oxyalky-lation susceptibility.

The product formed in acylation will vary with the particular polyaminomethyl phenol employed. It may be an ester or an amide depending on the available reactive groups. If, however, after forming the amide at a temperature between 140-250 C., but usually not above 200 C., one heats such products at a higher range, ap proximately 250280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid employed, the first mole of Water being evolved during arnidification. The product formed in such cases is believed to contain a cyclic amidine ring such as an imidazoline or a tetrahydropyrimidine ring.

Ordinarily the methods employed for the production of amino irnidazolines result in the formation of substantial amounts of other products such as amido imidazolines. However, certain procedures are Well known by which the yield of amino imidazolines is comparatively high as, for example, by the use of a polyamine in which one of the terminal hydrogen atoms has been replaced by a low molal alkyl group or an hydroxyalkyl group, and by the use of salts in which the polyamine has been converted into a monosalt such as combination with bydrochloric acid or paratoluene sulfonic acid. Other procedures involve reaction with a hydroxyalkyl ethylene diamine and further treatment of such imidazoline having a hydroxyalkyl substituent with two or more moles of ethylene imine. Other well known procedures may be employed to give comparatively high yields.

Other very useful derivatives comprise acid salts and quaternary salts, derived therefrom. Since the compositions contain basic nitrogen groups, they are capable of reacting with inorganic acids, for example hydrohalogens (HCl, HBr, HI), sulfuric acid, phosphoric acid, etc., aliphatic acids (acetic, propionic, glycolic, diglycolic, etc.), aromatic acids (benzoic, salicyclic, phthalic, etc.), and organic compounds capable of forming salts, for example, those having the general formula RX wherein R is an organic group, such as an alkyl group (e.g., methyl, ethyl, propyl, butyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, oleyl, octadecyl, etc.), cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.), aralkyl (e.g., benzyl, etc.), and the like, and X is a radical capable of forming a salt such as those derived from acids (e.g., halide sulfate, phosphate, sulfonate, etc., radicals). The preparation of these salts and quaternary compounds is well known to the chemical art. For example, they may be prepared by adding suitable acids (for example, any of those mentioned herein as tacylating agents) to solutions of the basic composition or by heating such compounds as alkyl halides with these compositions. Diacid and quaternary salts can also be formed by reacting alkylene dihalides, polyacids, etc. The number of moles of acid and quaternary compounds that may react With the composition of this invention, will of course, depend on the number of basic nitrogen groups in the molecule. These salts may be represented by the general formula N+ X", wherein N comprises the part of the compound containing the nitrogen group which has been rendered positively charged by the H or R of the alkylating compound and X represents the anion derived from the alkylating compound.

THE METHYLOL PHENOL As previously stated, the methylol phenols include monophenols and diphenols. The methylol groups on the phenol are either in one or two ortho positions or in the para position of the phenolic rings. The remaining phenolic ring positions are either unsubstituted or substituted with groups not interfering with the amine methylol condensation. Thus, the monophenols have 1, 2 or 3 methylol groups and the diphenols contain 1, 2, 3 or 4 methylol groups. 7

The following is the monophenol most advantageously employed:

CHZOH This compound, 2, 4, 6 trimethylol phenol (TMP) is available commercially in 70% aqueous solutions. The designation TMP is sometimes used to designate trimethylol propane. Apparently no confusion is involved, in light of the obvious differences.

A second monophenol which can be advantageously employed is:

where R is an aliphatic saturated or unsaturated hydrocarbon having, for example, 1-30 carbon atoms, for example, methyl, ethyl, propyl, butyl, sec-butyl, tertbutyl, amyl, tert-amyl, hexyl, tert-hexyl, octyl, nonyl, decyl, dodecyl, octo-decyl, etc., the corresponding unsaturated groups, etc.

The third monophenol advantageously employed is:

HOCHz CHZOH CHQOH where R comprises an aliphatic saturated or unsaturated hydrocarbon as stated above in the second monophenol, for example, that derived from cardanol or hydrocardanol.

The following are diphenol species advantageously employed:

One species is CHzOH CHQOH 1 I t R I HQOH CHzOH where R is hydrogen or a lower alkyl, preferably methyl.

A second species is:

where R has the same meaning as that of the second species of the monophenols and R is hydrogen or a lower alkyl, preferably methyl.

We can employ a wide variety of methylol phenols in the reaction, and the reaction appears to be generally applicable to the classes of phenols heretofore specified. Examples of suitable methylol phenols include:

Diphenols:

onion onion dnzon onion onion onzon HOGQHQOH (IIHZOH CHzOH (EH3 ICH3 CHBOH CHzOH CHzOH (3H3 (EH3 (3112011 GHzOH CHQOH HOCH -CH2 CH2OH l CHQOH OHzOH (IJH $11 HOCHz- CH2 CHaOH l C12H25 CrzHzs OH OH ifilHai HOCHz- (|3 CH2OH CH3 1 l CHzOH CHzOH OH OH I 3i HOCH (l3 CHzOH CH2:

CH3 CH3 CHzOH CHZOH CH3 I CHzOH CHzOH CHZOH (JIEHOH CHzOH CHZOH (|)H (l)H HOCHz-[ 1-3111 ]CH2OH CrzHza 0121125 (IJH2OH O CIHzOH ii Q -Q CHzOH CHzOH l fl l CHzOH CHzOH CHZOH CHzOH fi t O CHzOH CHaOH (FHzOH inger:

| (anion onion Examples of additional methylol phenols which can be employed to give the useful products of this invention are described in The Chemistry of Phenolic Resins]: by Robert W. Martin, Tables V and VI, pp. 32-39 (Wiley, 1956).

THE POLYAMINE As noted previously, the general formula for the polyamine is This indicates that a wide variety of reactive secondary polyamines can be employed, including aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines (provided the aromatic polyamine has at least one secondary amine which has no negative group, such as a phenyl group directly bonded thereto) heterocyclic polyamines and polyamines containing mixtures of the above groups. Thus, the term polyamine includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group on the heterocyclic radical as in the case of the following formula:

provided, of course, the polyamine has at least one secondary amino group capable of condensing with the methylol group. It also includes compounds which are totally heterocyclic, having a similarly reactive secondary amino group. It also includes polyamines having other elements besides carbon, hydrogen and nitrogen, for example, those also containing oxygen, sulfur, etc. As previously stated, the preferred embodiments of the present invention are the alkylene polyamines, the hydroxylated alkylene polyamines and the amino cyclic arnidines.

Polyamines are available commercially and can be prepared by Well-known methods. It is well known that olefin dichlorides, particularly those containing from 2 to 10 carbon atoms, can be reacted with ammonia or amines to give alkylene polyamines. If, instead of using ethylene dichloride, the corresponding propylene, butylene, amylene or higher molecular Weight dichlorides are used, one then obtains the comparable homologues. One can also use alphaomega dialkyl ethers such as ClCH OCH Cl ClCH CH OCH CH Cl, and the like. Such polyamines can be alkylated in the manner commonly employed for alkylating monoamines. Such alkylation results in products which are symmetrically or non-symmetrically alkylated. The symmetrically alkylated polyamines are most readily obtainable. For instance, alkyla-ted products can be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride, and the like and a polyamine having one or more primary amino groups. Such reactions result in the formation of hydrochloric acid, and hence the resultant product is an amine hydrochloride. The conventional treated with ethylene oxide method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain interrupted at least once by an oxygen atom. In other words, alkylation is accomplished by compounds which are essentially alkyloxyalkyl chlorides, as, for example, the following:

The reaction involving the alkylene dichlorides is not limited to ammonia, but also involves amines, such as ethylamine, propylamine, butylamine, octylamine, decylamine, cetylamine, dodecylamine, etc. Cycloaliphatic and aromatic amines are also reactive. Similarly, the reaction also involves the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylamine, etc. Furthermore, compounds derived by reactions involving alkylene dichlorides and a mixture of ammonia and amines, or a mixture of two different amines are useful. However, one need not employ a polyamine having an alkyl radical. For instance, any suitable polyalkylene polyamine, such as an ethylene polyamine, a propylene polyamine, etc., or similar oxalkylating agent are useful. Furthermore, various hydroxylated amines, such as monoethanolamine, monopropanolamine, and the like, are also treated with a suitable alkylene dichloride, such as ethylene dichloride, propylene dichloride, etc.

As to the introduction of a hydroxylated group, one can use any one of a number 'of well-known procedures such as alkylation, involving a chlorhydrin, such as ethylene chlorhydrin, glycerol chlorhydrin, or the like. Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides previously described. Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like. Glycide is advantageously employed. The type of reaction just referred to is well known and results in the introduction of a hydroxylated or polyhydroxylated radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarbon atom; for instance, instead of using the chlorhydrin corresponding to ethylene glycol, one employs the chlorhydrin corresponding todiethylene glycol. Similarly, instead of using the chlorhydrin corresponding to glycerol, one employs the chlorhydrin corresponding to diglycerol.

From the above description it can be seen that many of the above polyamines can be characterized by the general where the Rs, which are the same or different, comprise hydrogen, alkyl, cycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylated alkyloxyal'kyl, etc., radical, x is zero or a whole number of at least one, for example 1 to 10, but preferably 1 to 3, provided the polyamine contains at least one secondary amino group, and n is a whole number, 2 or greater, for example 2 10, but preferably 2-5. Of course, it should be realized that the amino or hydroxyl group may be modified by acylation to form amides, esters or mixtures thereof, prior to the methylolamino condensation provided at least one active secondary amine group remains on the molecule. Any of the suitable acylating agents herein described may be employed in this acylation. Prior acylation of the amine can advantageously be used instead of acylation subsequent to amine condensation.

pk 0-6 but preferably 0-1.

10 A particularly useful class of polyamines is a class of branched polyamines. These branched polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene -RNH: it

N Hg y wherein R is an alkylene group such as ethylene, propylene, butylene and other homologues (both straight chained and branched), etc., but preferably ethylene; and

x, y and z are integers, x being for example, from 4 to 24 or more but preferably 6 to 18, y being for example 1 to 6 or more but preferably 1 to 3, and 2 being for exam- The x and y units may be sequential, alternative, orderly or randomly distributed.

The preferred class of branched polyamines includes those of the formula where n is an'integer, for example 1-20 or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).

The particularly preferred branched polymines are presented by the following formula:

The radicals in the brackets may be joined in a headto-head or a head-to-tail fashion. Compounds described by this formula wherein n=1-3 are manufactured and sold by Dow Chemical Company as Polyamines N-400, N-800, Nl200, etc. Polyamine N-400 has the above formula wherein n=1 and was the branched polyamine employed in all of the specific examples.

The branched polyamines can be prepared by a wide variety of methods. One method comprises the reaction of ethanolamine and ammonia under pressure over a fixed bed of a metal hydrogenation catalyst. By controlling the conditions of this reaction one can obtain various amounts of piperazine and polyamines as well as the branched chain polyalkylene polyamine. This process is described in Australian Patent No. 42,189 and in the East German Patent 14,480 (March 17, 1958) reported in Chem. Abstracts, August 10, 1958, 14129.

The branched polyamines can also be prepared by the following reactions:

12 The above polyamines modified with higher molecular weight aliphatic groups, for example, those having from Variations on the above procedure can produce other branched polyamines.

The branched nature of the polyamine imparts unusual properties to the polyarnine and its derivatives. Cyclic aliphatic polyamines having at least one secondary amino group such as piperazine, etc., can also be employed.

It should be understood that diarnines containing a secondary amino group may be employed. Thus, where x in the linear polyalkylene amine is equal to zero, at least one of the Rs would have to be hydrogen, for example, a compound of the following formula:

If"- 0 H2 CHr-NI'I H Suitable polyarnines also includes polyamines wherein the alkylene group or groups are interrupted by an oxygen radical, for example,

or mixtures of these groups and alkylene groups, for example,

where R, n and x has the meaning previously stated for the linear polyamine.

For convenience the aliphatic polyamines have been classified as nonhydroxylated and hydroxylated alkylene polyamino amines. The following are representative members of the nonhydroxylated series:

Diethylene triamine,

Dipropylene triarnine,

Dibutylene triamine, etc.

Triethylene tetramine,

Tripropylene tetramine,

Tributylene tetramine, etc.,

Tetraethylene pentamine,

Tetrapropylene pentamine,

Tetrabutylene pentarnine, etc.,

Mixtures of the above,

Mixed ethylene, propylene, and/0r butylene, etc., polyamines and other members of the series.

8-30 or more carbon atoms, a typical example of which 1s where the aliphatic group is derived from any suitable source, for example, from compounds of animal or vegetable origin, such as coconut oil, tallow, tall oil, soya, etc., are very useful. In addition, the polyamine can con tain other alkylene groups, fewer amino groups, additional higher aliphatic groups, etc., provided the polyamine has at least one reactive secondary amino group. Compositions of this type are described in US. Patent 2,267,205.

Other useful aliphatic polyamines are those containing substituted groups on the chain, for example, aromatic groups, heterocyclic groups, etc., such as a compound of the formula Where R is alkyl and Z is an alkylene group containing phenyl groups on some of the alkylene radicals since the phenyl group is not attached directly to the secondary amino group.

In addition, the alkylene group substituted with a hydroxy group N CzH5N CzHaN H H H CH3 CH3 N C 2114 O C2H4N Examples of polyamines having hydroxylated groups include the following:

N O ZHAN C 2H4N H HOC2H4 HO C2H4 HO C2114 HOCzH;

ENE

wherein R is a hydrocarbon group,

where x: 1-5.

2-undecylimidazoline 2-heptadecylimidazoline 2-oleylimidazoline l-N-decylaminoethyl,2-ethylimidazoline 2-methyl, 1-hexadecylaminoethylaminoethylimidazoline 1-dodecylaminopropylimidazoline l- (stearoyloxyethyl) aminoethylimidazoline l-stearamidoethylaminoethylimidazoline 2-heptadecyl,4-5-dimethylimidazoline 1-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazoline Z-heptadecyl,l-methylaminoethyl tetrahydropyrimidine 4-methyl,2-dodecyl,l-methylaminoethylaminoethyl tetrahydropyrimidine As previously stated, there must be reacted at least one mole of polyamine per equivalent of methylol group. The upper limit to the amount of amine present will be determined by convenience and economics, for example, 1 or more moles of polyamine per equivalent of methylol group can be employed.

The following examples are illustrative of the preparation of the polyaminomethylol phenol condensate and are not intended for purposes of limitation.

The following general procedure is employed in preparing the polyamine-rnethylol condensate. The methylolphenol is generally mixed or slowly added to the polyarnine in ratios of 1 mole of polyamine per equivalent of methylol group on the phenol. However, where the polyamine is added to the methyl-ophenol, addition is carried out below 60 C. until at least one mole of poly'amine per methylol group has been added. Enough of a suitable azeotroping agent is then added to remove water (benzene, toluene, or xylene) and heat applied. After removal of the calculated amount of water from the reaction mixture one mole of water per equivalent of methylol group) heating is stopped and the azeotroping agent is evaporated oif under vacuum. Although the reaction takes place at room temperature, higher temperatures are required to complete the reaction. Thus, the temperature during the reaction generally varies from 160 C. and the time from 4?A hours. In general, the reaction can be effected in the lower time range employing higher temperatures. However, the time test of completion of reaction is the amount of water removed.

Example 1a This example illustrates the reaction of a methylolmonophenol and a polyamine. A liter flask is employed with a conventional stirring device, thermometer phase separating trap condenser, heating mantle, etc. 70% aqueous 2,4,6 trimethylol phenol which can be prepared by conventional procedures or purchased in the open market, in this instance, the latter, is employed. The amount used is one gram mole, i.e., 182 grams, of anhydrous trimethylol phenol in 82 grams of water. This represents three equivalents of methylol groups. This solution is added dropwise with stirring to three gram moles (309 grams) of diethylene triamine dissolved in 100 ml. of xylene over about 30 minutes. An exothermic reaction takes place at this point but the temperature is maintained below approximately 60 C. The temperature is then raised so that distillation takes place with the removal of the predetermined amount of water, i.e., the water of solution as well as water of reaction. The water of reaction represents 3 gram moles or 54 grams.

The entire procedure including the initial addition of the trimethylol phenol until the end of the reaction is approximately 6 hours. At the end of the reaction period the xylene is removed, using a vacuum of approximately 80 mm. The resulting product is a viscous water-soluble liquid of a dark red color.

Example 28a This example illustrates the reaction of a methylolmonophenol and a branched polyamine. A one liter flask is employed equipped with a conventional stirring device, thermometer, phase separating trap, condenser, heating mantle, etc. Polyamine N400, 200 grams (0.50 mole), is placed in the flask and mixed with 150 grams of xylene. To this stirred mixture is added dropwise over a period of 15 minutes 44.0 grams (0.17 mole) of a 70% aqueous solution of 2,4,6-trimethylol phenol. There is no apparent temperature change. The reaction mixture is then heated to 140 C., refluxed 45 minutes, and 24 milliliters of water is collected (the calculated amount of water is 22 milliliters). The product is a dark brown liquid (as a 68% xylene solution).

Example 2d This example illustrates the reaction of a methylol diphenol.

One mole of substantially water-free CHZOH CH OH l CH OH CHQOH and 4 moles of triethylenetetramine in 300 ml. of xylene are mixed with stirring. Although an exothermic reaction takes place during the mixing, the temperature is maintained below 60 C. The reaction mixture is then heated and azeotroped until the calculated amount (72 g.) of water is removed (4 moles of water of reaction). The maximum temperature is 150 C. and the total reaction time is 8 hours. Xylene is then removed under vacuum. The product is a viscous Watersoluble liquid.

Example b In this example, 1 mole of substantially water-free is reacted with 2 moles of Duomeen S (Armour Co.),

where R is a fatty group derived from soya oil, in the manner of Example 2a. Xylene is used as both solvent l d and azeotroping agent. The reaction time is 8 hours and the maximum temperature 150-160 C.

Example 28b This experiment is carried out in the same equipment as is employed in Example 28a except that a 300 milliliter flask is used. Into the flask is placed 50 grams of xylene and 8.4 grams (0.05 mole) of 2,6-dimethylol-4- methylphenol are added. The resulting slurry is stirred and warmed up to C. Polyamine N-400, 40.0 grams (0.10 mole) is added slowly over a period of 45 minutes. Solution takes place upon the addition of the polyamine. The reaction mixture is refluxed for about 4 hours at C. and 1.8 milliliters of water is collected, the calculated amount. The product, as a xylene solution, is a brown liquid.

Example 29b This experiment is carried out in the same equipment and in the same manner as is employed in Example 28b. To a slurry of 10.5 grams 0.05 mole) of 2,6-dimethylol-4- tertiarybutylphenol in 50 grams of xylene, 40 grams (0.10 mole) of Polyamine N-400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 4 hours with the collection of 1.6 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is reddish brown.

Example 30b This experiment is carried out in the same equipment and in the same manner as is employed in Example 28b. To a slurry of 14.0 grams of 2,6-dimethylol-4-nonylphenol in 50 milliliters of benzene, 40.0 grams (0.10 mole) of Polyamine N400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 6 hours with the collection of 1.8 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is dark brown.

The following amino-methylol condensates shown in Tables LIV are prepared in the manner of Examples 10, 2d, and 5b. In each case one mole of polyamine per equivalent of methylol group on the phenol is reacted and the reaction carried out until, taking into consideration the water originally present, about one mole of water is removed for each equivalent of methylol group present on the phenol.

The pH of the reaction mixture is determined solely by the reactants (i.e., no inorganic base, such as Ca(OH) NaOH, etc. or other extraneous catalyst is present). Examples 1a, 2d, and 5b are also shown in the tables. Attempts are made in the examples to employ commercially available materials where possible.

In the following tables the examples will be numbered by a method which will describe the nature of the product. The polyamine-methylol condensate will have a basic number, for example, 1a, 4b, 6c, 4d, wherein those in the A series are derived from TMP, the B series from DMP, the C series from trimethylol cardanol and side chain hydrogenated cardanol (i.e., hydrocardanol), and the d series from th tetramethylol diphenols. The basic number always refers to the same amino condensate. The symbol A before the basic number indicates that the polyamine had been acylated prior to condensation. The symbol A after the basic number indicates that acylation takes place after condensation.

A25a means that the 25a (amino condensate) was prepared from an amine which had been acylated prior to condensation. However, IOaA means that the condensate was acylated after condensation. The symbol 0 indicates oxyalkylation. 'I hus 10aAO indicates that the amine condensate 10a has been acylated 10aA), followed by oxyalkylation. lOaAOA means that the same condensate, 10a, has been acylated (l0aA), then oxyalkylated (IOaAO) and then acylated. In other words, these symbols indicate both kind and order of treatment.

TABLE IV Continued Example R Polyamine 18d do Duomeen T (Armour 00.)

H RNCHzOH CH2NH (R derived from tallow) 19d do Oxyethylated Duomeen S H O H4OH RNCH2CHOHN 20d do Oxyethylated Duomeen T H OzHlOH R-N-CHzCHzCHzN 21d do Amine ODT (Monsanto) H C nHgs-fi- C zH4N-C gH4HNg 22d do Oxyethylated Amine ODT H rC7H4OH C12H25 C2H4NC2H4N 23d .do N-(2-hydroxyethyl)-2-methy1-1,2-propanediamine 23d do N-methyl ethylene diamine.

THE ACYLATING AGENT As in the reaction between the methylol phenol and the secondary amine, acylation is also carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. F or example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.

A wide variety of acylating agents can be employed. However, strong acylating agents such as acyl halides, or acid anhydrides should be avoided since they are capable of esterifying phenolic hydroxy groups, a feature which is undesirable.

Although a wide variety of carboxylic acids produce excellent products, in our experience monocarboxy acids having more than 6 carbon atoms and less than 40 carbon atoms give most advantageous products. The most common examples include the deter-gent forming acids, i.e., those acids which combine with alkalies to produce soap or soaplike bodies. The detergent-forming acids, in turn, include naturally-occurring [fatty acids, resin acids, such as abietic acid, naturally occurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are different in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromat-ic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, angelic, tiglic, pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octenoic acids, the nonenoic acids, the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodecenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitolcic acid, the heptadecenoic acids, the octadecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetracosenoic acids, and the like.

Examples of deinoic acids are the pentadenoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linoleic acid, eleostearic acid, pseudoeleostearic acid, and the like.

Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxymyristic acids, the hydroxypentadecanoic acids, the hydroxypalmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid ricinelardic acid, hydroxyoctadecenoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydrocarpic and chaulmoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fenholic acids, and the like.

Examples of aromatic monocarboxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids, the xylenic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, Whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan Wax, Japan wax, coccerin and carnauba Wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic aid, psyllastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from paraflin Wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesacenic, citraconic, glutaconic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof, e.g., alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than tWo carboxylic groups are hemimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric and polymeric acids, for example, dilinoleic trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as esters, glycerides, etc. can be employed in place of the free acid.

The moles of acylating agent reacted with the polyaminomethyl compound will depend on the number of acetylation reactive positions contained therein as well as the number of moles one wishes to incorporate into the molecule. We have advantageously reacted 1 to 15 moles of acylating agent per mole of polyaminophenol, but preferably 3 to 6 moles.

The following examples are illustrative of the preparation of the acylated polyaminomethyl phenol condensate.

The following general procedure is employed in acylating. The condensate is mixed with the desired ratio of acid and a suitable azeotroping agent is added. Heat is then applied. After the removal of the calculated amount of Water (1 to 2 equivalents per mole of acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from 80200 C. (except where the formation of the cyclic amidine type structure is desired and the maximum temperature is generally 200 280 C.). The times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 3aA In a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle, 697 grams of 312 (one mole of the TMP-tetraethylene pentamine reaction product) is dissolved in 600 ml. of xylene. 846 grams of oleic acid (3 moles) is added to the TMP-polyamine condensate with stirring in ten minutes. The reaction mixture was then heated gradually to about 145 in half an hour and then held at about 160 over a period of 3 hours until 54 grams (3 moles) of Water is collected in the side of the tube. The solvent is then removed With gentle heating under a reduced pressure of approximately 20 mm. The product is a dark brown viscous liquid with a nitrogen content of 14.5%.

Example 3aA The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 90 grams (5 moles) of water is removed instead of 54 grams. Infrared analysis of the product indicates the presence of a cyclic amidine ring.

Example 711A The reaction product of Example 7a (TMP and oxyethylated Duomeen S) is reacted with palmitic acid in the manner of Example 3aA. A xylene soluble product is formed.

The following examples of acylated polyaminomethyl phenol condensates are prepared in the manner of the above examples. The products obtained are dark viscous liquids Example 28aA Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle, is placed a xylene solution of the product of Example 28a containing 98.0 grams (0.05 mole) of Example 28bA Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle is placed a xylene solution of the product of Example 28b containing 35.0 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-methylphenol and Polyamine N400 and about 20 grams of xylene. To this solution is added with stirring 14.1 grams (0.05 mole) of oleic acid. The reaction mixture is heated at reflux for 4.5 hours at a maximum temperature of 183 C. and 1.0 milliliters of water is collected, the calculated amount of water for amide formation being 0.9 milliliter. The product is a dark burgundy liquid (as 70.5% xylene solution) le 29bA This experiment is performed in the same equipment and in the same manner as employed in Example 28bA. Into the flask is placed a xylene solution of the product of Example 29b containing 40.9 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-tertiarybutyl phenol and Polyamine N-400 and about 47 grams of xylene. To this solution is added with stirring 7.2 grams (0.05 mole) of octanoic acid. The reaction mixture is heated at reflux for 3.75 hours at a maximum temperature of 154 C. and 1.3 milliliters of water is collected. The calculated amount of water for amide formation is 0.9 milliliter. The product as a 49.82 percent xylene solution was brown.

Example 30bA This experiment is performed in the same manner and in the same equipment as is employed in Example 28bA. Into the flask is placed a xylene solution of the product of Example 30b containing 39.6 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-nonylphenol and Polyamine N-400 and about 32 grams of xylene. To this solution is added with stirring 14.2 grams (0.05 mole) of stearic acid. The reaction mixture is heated at reflux for 4 hours at a maximum temperature of 160 C. and 1.0 milliliter of water is collected. The calculated amount of water for amide formation is 0.9 milliliter. The product as a 62.5% xylene solution is a brown liquid.

TABLE V.ACYLATED PRODUCTS OF TABLE I Grams of acid per Grams of Example Acid gram-mole water reof eondenmoved sate Oleio 846 54 Nonanoic 316 36 Oleie 846 54 dn 846 Stearie 852 54 Laurie- 600 54 Myristie- 684 54 Palmitie. 768 54 Propanoie 222 54 Dimeric 1, 800 54 10 A OlPiP 34 54 A ..d0 846 54 1241A Sunaptic acid 990 54 1 A 846 54 15aA Palmitic 1, 536 108 1611 A Ole-iv 846 54 17a A do 1, 692 108 ISaA dO 1, 692 108 IQnA do 846 54 23" A Acetic 180 54 2811A Laurie 600 Also employed in ex- ,TABLE VL-ACYLATED PRODUCTS OF TABLE II Grams of acid used Grams of Example Acid per .gramwater remole of moved condensate hi See footnotes at bottom of Table V.

TABLE VII.ACYLATED PRODUCTS OF TABLE III Grams of acid used Grams of Example Acid per gramwater removed See lootnotes at bottom of Table V.

TABLE VIII.--ACYLATED PRODUCTS 013 TABLE IV Grams of acid used Grams of per gramwater Example Acid removed See footnotes at bottom of Table V.

Reference has been made and reference will be continued to be made herein to oxyalkylation procedures. Such procedures are concerned with the use of monoepoxides and principally those available commercially at low cost, such as ethylene oxide, propylene oxide and butylene 'o'xide, octylene oxide, styrene oxide, etc.

Oxyalkylation is well known. For purpose of brevity reference is made to Parts 1 and 2 of US. Patent No. 2,792,371, dated May 14, 1957, to Dickson in which particular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive information as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.

The following examples illustrate oxyalkylation.

Example 10A 0 The reaction vessel employed is a 4 liter stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means, etc., which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 rpm. Into the autoclave is charged 1230 grams (1 mole) of MA, and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring started immediately, and heat applied. The temperature is allowed to rise to approximately C. at which time the addition of ethylene oxide is started. Ethylene oxide is added continuously at such speed that it is absorbed by the reaction mixture -as added. During the addition 132 grams (3 moles) of ethylene oxide is added over 2%. hours at a temperature of 100 C. to C. and a maximum pressure of 30 psi.

Example 10110;

The reaction mass of Example 1A0 is transferred to a larger autoclave (capacity 15 liters) similarly equipped. Without adding any more xylene the procedure is repeated so as to add another 264 grams (6 moles) of ethylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.

Example JaAO In a third step, another 264 grams (6 moles) of ethylene oxide is added to the product of Example 1aAO The reaction slows up and requires approximately 6 hours, using the same operating temperatures and pressures.

Example 1aA0 At the end of the third step the autoclave is opened and 25 grams of sodium methylate is added, the autoclave is flushed out as before, and the fourth and final oxyalkylation is completed, using 1100 grams (25 moles) of ethylene oxide. The oxyalkylation is completed within 6 /2 hours, using the same temperature range and pressure as previously.

Example 1aA0 The reaction vessel employed is the same as that used in Example laAO. Into the autoclave is charged 1230 g. (1 mole) of 1aA and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring is started immediately, and heat is applied. The temperature is allowed to rise to approximately 100 C. at which time the addition of propylene oxide is started. Propylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 174 g. (3 moles) of propylene oxide are added over 2 /2 hours at a temperature of 100 to 120 C. and a maximum pressure of 30 lbs. p.s.i.

Example laAO The reaction mass of Example 1aAO is transferred to a larger autoclave (capacity 15 liter-s). The procedure is repeated so as to add another 174 g. (3 moles) of propylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.

Example laAO- At the end of the second step (Example 1aAO the autoclave is opened, 25 g. of sodium methylate is added, and the autoclave is flushed out as before. Oxylalkyl- 2? ation is continued as before until another 522 g. (9 moles) of propylene oxide are added. 8 hours are required to complete the reaction.

The following examples of oxyalkylation are carried out in the manner of the examples described above. A catalyst is used in the case of oxyethylation after the initial 15 moles of ethylene oxide are added, while in the case of oxypropylation, the catalyst is used after the initial 6 moles of oxide are added. In the case of oxybutylation, oxyoctylation, oxystyrenation, etc. the catalyst is added at the beginning of the operation. In all cases the amount of catalyst is about 1 /2 percent of the total reactant present. The oxides are added in the order given reading from left to right. The results are presented in the following tables:

TABLE IX.-TI-IE OXYALKYLATED PRODUCTS OF TABLE I Grams of oxide added per gram-mole of condensate EtO PrO BuO Oetylene oxide Styrene oxide TABLE X.THE OXYALKYLATED PRODUCTS OF v TABLE II Grams of oxide added per gram-mole of condensate Example PrO BuO Oetylene oxide Styrene oxide EtO TABLE XII.THE OXYALKYLATED PRODUCTS OF TABLE IV Grams of oxide added per gram-mole of condensate Example EtO PrO BuO Octylcne oxide Styrene oxide TABLE XIII.THE OXYALKYLATED PRODUCTS OF TABLE V Grams of oxide added per gram-mole of condensate Example EtO PrO B110 Octylene oxide Styrene oxide TABLE XIV.THE OXYALKYLATED PRODUCTS 0F TABLE VI TABLE XI.THE O XYALKYLATED PRODUCTS OF TABLE III Grams of oxide added per gram-mole oi condensate Grams of oxide added per gram-mole oi acylated product Example EtO PrO BuO Oetylene Styrene oxide oxide Example PrO BuO Styrene oxide EtO Octylene oxide TABLE X'tC-TI-IE OXYALKYLATED PRODUCTS OF TABLE VI product Example EtO PrO BuO Octylene Styrene oxide oxide TABLE XVI.THE OXYALKYLATED PRODUCTS OF TABLE VII Grams of oxide added per gram-mole of acylated product Example EtO PrO BuO Octylene Styrene oxide oxide Since the oxyalkylated, and the acylated and oxyalkylated products have terminal hydroxy groups, they can be acylated. This step is carried out in the manner previously described for acylation. These examples are illustrative and not limiting.

Example IaOA One mole (919 grams) of 1:10 mixed with 846 grams (three moles) of oleic acid and 300 ml. xylene. The reaction mixture is heated to about ISO-160 C. over a period of 2 hours until 54 grams (3 moles) of water are removed. Xylene is then removed under vacuum. The product laOA is xylene soluble.

Example 1 aA A The process of the immediately previous example is repeated using laAO. The product laAOA is xylene soluble.

Additional examples are presented in the following tables. All of the products are dark, viscous liquids.

Grams of oxide added per gram-mole of acylated 5 TABLE XVII.THE ACYLATEDggODUCTS OF TABLES IX,

Grams water removed Example Acid MMOJHH HHHHHHHHHHHb-H- mcimoooooooooooocooooooooooooomonoo TABLE XVIII.THE AOYLA'IED PRODUCTS OF TABLES XIII, XIV, XV, XVI

Grams of acid per Grams Example Acid gram-mole water of oxyremoved alkylated product;

laA 0A 282 18 284 18 282 18 daAOA 284 18 2811A 0A 200 18 MA 0A 282 18 2bAOA 282 18 3bA 0A 284 18 4bA OA 282 18 28bA OA 284 18 29bAOA 564 36 282 18 228 18 200 18 282 18 4cAOA 282 18 103A OA 568 36 2dAOA 568 36 564 36 0A 564 36 INHIBITING FOAM This phase of the invention relates to the use of the aforementioned compositions in a process for reducing or destroying foam or inhibiting its formation in environments of either an aqueous or a non-aqueous nature.

Foams occur as undesirable, incidental features in many industrial processes. The theory of their formation is not highly developed so that hypotheses on which foam reduction or destruction processes might be based are difficult to formulate As a consequence the effectiveness of foam-destroying agents are difficult to predict Our novel process of reducing or destroying foams and of preventing their formation appears to be relatively general in applicability in that it may be used with compositions comprising aqueous materials or solutions, compositions comprising nonaqueous materials, such as hydrocarbon liquids, and compositions comprising mixtures of aqueous and nonaqueous media. Our process consists in subjecting a foaming or potentially-foaming composition to the action of a small proportion of the reagents of this invention as anti-foamers, thereby causing the foaming properties of the liquid to be diminished, suppressed or destroyed, In applying our process to the reduction or destruction of a foam, the reagent is poured or sprayed or dripped into the body of foam on top the liquid, as desired; and the foam breaks and is destroyed or reduced, substantially at once, as a consequence of such addition of said reagent. Adding the reagent to the liquid underlying such already-formed foam is also practicable. In applying our process to the prevention of foaming, the reagent is admixed, in some small proportion, with a potentially-foaming liquid, by any desired or suitable procedure. The ability of the system to foam is destroyed or at least materially reduced by such addition of said reagent.

It is usual-1y convenient to dilute our reagents during manufacture or before use with some suitable solvent. Solvents generally suitable for incorporation into our reagent include: water; petroleum hydrocarbons, like gasoline, kerosene, stove oil, aromatic solvent; coal tar products, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil; alcohols, particularly aliphatic alcohols like methyl, ethyl, isopropyl, b-utyl, hexyl, octyl, etc. Miscellaneous solvents, such as piper oil, carbon tetrachloride, etc., may be employed. Sometimes other factors such as whether it imparts an objectionable odor to the deformed composition or to the products into which it finds its way will determine the choice of solvent. In general, the amount of finished anti-foamer reagent employed is so small that considerable tolerance of undesirable properties in a solvent exists.

The mixture of active ingredient and solvent is stirred until homogeneous. We prefer to employ a petroleum distillate in the proportion of to of the finished product, by volume, although water is an excellent solvent in some instances.

We desire to point out that the superiority of the reagent contemplated by our process is based upon its ability to reduce or destroy foam, or to prevent foam formation, in certain foaming or potentially foaming compositions more advantageously and at lower cost than is possible with other reagents or processes. Our reagents are useful in controlling foams in many different types of systems, aqueous and non-aqueous. They will control foams encountered in the manufacture of alkaline hypochlorite bleaches. They are effective in controlling foam in petroleum refining operations. They are effective in inhibiting foam in a gas-treating system, in which a mixture of glycols and alkanolamines is used to dehydrate and purify natural gas.

We can apply our reagents to the control of foam in protein adhesives solutions, such as casein and soybean adhesives, as used in the plywood industry, in papermaking, latex adhesives, printing inks, aqueous emulsion paints, which all produce foams which are amenable to our reagents.

In the foregoing description we have made it clear that our reagents may be used to reduce, destroy, or prevent foam. In the appended claims we have used the word inhibit to include all these corrective and preventive aspects of our process and reagents.

The procedures employed in practicing our process are numerous. The following description will illustrate sever-al techniques commonly employed. It should be understood that the claims are not limited to the procedures described, and that our process consists broadly in bringing into contact by any suitable means our reagent and the foam or the potentially foaming composition.

In controlling foam in a glycol-amine gas treating plant handling natural gas, the glycol-amine mixture has a volume of about 2,000 gallons and make-up is about 2,000 gallons a month. The reagents are injected into the liquid mixture in the return-line from the stripping operation, by means of an electrically-powered proportioning pump of conventional design. The feed rate is less than 1 quart daily. Foam difficulties in the system are satisfactorily controlled by procedure.

In sewage plants, for example, in activated sludgeprocess plants, foam is frequently a serious problem in aeration basins and elsewhere. In one such plant, our reagents will control foam when sprayed into the head of foam, or when sprayed into or simply poured into the liquid in such basins. The foam-inhibiting efiect appears to persist quite satisfactorily.

Determination of the optimum or minimum amount of our foam-inhibiting reagents to be used in any application is accomplished in different ways. Small portions of the potentially foaming liquid are added to test bottles, different small proportions of our reagent added, and the chemicalized samples shaken for a short time. Simple observation of the relative speed and completeness of foam destruction should permit selection of the best reagent proportion to be applied on the large scale. The easiest way to determine the amount of reagent required is to introduce it into the foaming or potentially foaming liquid in a fairly large proportion, e.g., 1%, and then to reduce the reagent feed rate until foam destruction is just being accomplished satisfactorily. Usually foam destruction is directly proportional to the amount of reagent used, at least up to about =1% of reagent. In a few instances, it may be found that using more or less reagent than an optimum proportion will give inferior results.

If the proportions of reagents to be employed in the above test are very small, it may be desirable to determine the optimum proportions of foaming composition and anti-foamer by introducing the latter into the sample of foaming liquid in the form of a solution in a suitable solvent.

Our process is equally applicable to systems in which a foam is already in existence and to systems which are potentially foaming composition, in that they have the property of producing foams when agitated or mixed with air or some other suitable gas. Destruction, reduction and prevention are substantially equivalent actions. It is impossible to determine whether the reagent does in fact prevent the formation of the initial laminae of foam or whether such initial laminae are destroyed by the reagent before subsequent laminae of sufficient stability to produce a foam can be superimposed thereon. By foaming composition in the appended claims we mean a composition which is either actually foaming or which is capable of producing a foam under suitable conditions, e.g., by simply passing air through it.

It most instances, our reagents are effective to the extent that they destroy an existing foam substantially completely. -In some instances, as when too little reagent is used and foam reduction may be slow or even incomplete, we intend that the description and our invention relate both to complete destruction and to partial destruction of foams.

The proportions of our reagents required to be employed appear to vary widely. However, we generally use our reagent in amounts 1% by volume or less of the foaming composition. Usually, the amounts required will be between 0.1% and 0.0001%, by volume based on the volume of the foaming composition.

Our present reagents may be used in conjunction with any other effective and compatible anti-foamer. It should also be stated that they are useful in conjunction with foam-inhibiting processes which are mechanical or electrical in character, rather than chemical. For example, some foams may be effectively destroyed by water sprays or jets. Incorporation of a small proportion of our reagents into such water sprays increase their effectiveness. US. Patent No. 2,240,495, to Dillon et al., dated May 6, 1941, relates to a process for resolving foam by means of a high electrical potential. Incorporation of a small proportion of our present reagents into the foaming liquid increases the effectiveness of such electrical processes.

The following examples are presented to illustrate our invention.

A foam is effected in a graduated cylinder containing mineral oil by bubbling nitrogen into the system. At equilibrium the height of the foam is measured and when the nitrogen is shut ofif, the time for the foam to drop is also measured. This procedure is repeated employing the compounds shown in the following table in ratios of 33 0.001% by volume in the oil. The presence of these compounds eifectively reduces the height of the foam that is formed and aids in its elimination.

ANTI-FOAMING AGENT Reactants (grams) Order of addition of oxides as indicated by alphabet Pl'O (580)-1-(13) EtO (220).

2)+(A) PrO (2030)+(B) EtO (440).

2)+(A) BuO (1080)+(B) Eto (440 )+(A) PrO (1160)+(B) EtO (660).

1211 (800)+Octylene Oxide (1280).

28a (1960)+Pr0 (580).

2811A (2440)+(A) BuO 720 (B) PrO 174 1% i3320)+(A) PrO 348 (B) EtO (440).

28aAOA. 281) (1400) +P1O (348) 28 bA 1. A process for inhibiting foam characterized by subjecting a foaming composition to a member selected from the group consisting of:

(1) acylated, (2) oxyalkylated, (3) acylated then oxyalkylated, (4) oxyalkylated then acylated, (5) acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols characterized by reacting a preformed methylol phenol having one to four methylol groups in the 2, 4, 6 position with a polyamine containing at least one secondary amine group in amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol until one mole of water per equivalent of methylol group is removed, in the absence of an extraneous catalyst; and then reacting the thus formed monomeric polyaminomethyl phenol with a member selected from the group consisting of (1) an acylation agent, (2) an oxyalkylation agent, (3) an acylation then an oxyalkylation agent, (4) an oxyalkylation then an acylation agent, and (5) an acylation then an oxyalkylation and then an acylation agent the preformed methylol phenol having only functional groups selected from the class consisting of methylol groups and phenolic hydroxyl groups, the polyamine having only functional groups selected from the class consisting of primary amino groups, secondary amino groups and hydroxyl groups,

the acylation agent having up to 40 carbon atoms and being selected from the class consisting of unsubstituted carboxylic acids, unsubstituted hydroxy carboxylic acids, unsubstituted acylated hydroxy carboxylic acids, lower alkanol esters of unsubstituted carboxylic acids, glycerides of unsubstituted carboxylic acids, unsubstituted carboxylic acid chlorides and unsubstituted carboxylic acid anhydrides, and the oxalkylation agent being selected from the class consisting of alpha-beta alkylene oxides and styrene oxide.

2. The process of claim 1 where the preformed methylol phenol has all available ortho and para positions substituted With methylol groups.

3. The process of claim 1 where the polyamine is an aliphatic polyamine.

4. The process of claim 1 Where the polyamine is polyalkylene polyamine.

5. The process of claim 1 where the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms.

6. The process of claim 1 where the oxyalkylation agent is at least one 1,2 alkylene oxide having 2 to 4 carbon atoms.

7. The process of claim 1 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms, and the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms.

8. The process of claim 1 where the member prepared is (1) an oxyalkylated monomeric polyaminomethyl phenol, the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, and the oxyalkylation agent is at least one 1,2-alkylene oxide.

9. The process of claim 8 where the polyamine is diethylene triamine and the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms.

10. The process of claim 8 where the polyamine is triethylene tetramine and the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms.

11. The process of claim 9 where the 1,2-alkylene oxide is propylene oxide.

12. The process of claim 10 where the 1,2-alkylene oxide is propylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,701,239 Ryznar Feb. 1, 1955 2,723,959 Jacoby et a1 Nov. 15, 1955 2,748,085 Monson May 29, 1956 2,748,086 Monson May 29, 1956 2,748,087 Monson May 29, 1956 2,748,089 Monson May 29, 1956 2,946,759 Gallant July 26, 1960 FOREIGN PATENTS 999,437 France Oct. 3, 1951 

1. A PROCESS FOR INHIBITING FOAM CHARACTERIZED BY SUBJECTING A FOAMING COMPOSITION TO A MEMBER SELECTED FROM THE GROUP CONSISTING OF: (1) ACYLATED, (2) OXYALKYLATED, (3) ACYLATED THEN OXYALKYLATED, (4) OXYALKYLATED THEN ACYLATED, (5) ACYLATED, THEN OXYALKYLATED AND THEN ACYLATED, MONOMERIC POLYAMINOMETHYL PHENOLS CHARACTERIZED BY REACTING A PREFORMED METHYLOL PHENOL HAVING ONE TO FOUR METHYLOL GROUPS IN THE 2, 4, 6 POSITION WITH A POLYAMINE CONTAINING AT LEAST ONE SECONDARY AMINE GROUP IN AMOUNTS OF AT LEAST ONE MOLE OF SECONDARY POLYAMINE PER EQUIVALENT OF METHYLOL GROUP ON THE PHENOL UNTIL ONE MOLE OF WATER PER EQUIVALENT OF METHYLOL GROUP IS REMOVED, IN THE ABSENCE OF AN EXTRANEOUS CATALYST; AND THEN REACTING THE THUS FORMED MONOMERIC POLYAMINOMETHYL PHENOL WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF (1) AN ACYLATION AGENT, (2) AN OXYALKYLATION AGENT, (3) AN ACYLATION THEN AN OXYALKYLATION AGENT, (4) AN OXYALKYLATION THEN AN ACYLATION AGENT, AND (5) AN ACYLATION THEN AN OXYALKYLATION AND THEN AN ACYLATION AGENT THE PREFORMED METHYLOL PHENOL HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF METHYLOL GROUPS AND PHENOLIC HYDROXYL GROUPS, THE POLYAMINE HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF PRIMARY AMINO GROUPS, SECONDARY AMINO GROUPS AND HYDROXYL GROUPS, THE ACYLATION AGENT HAVING UP TO 40 CARBON ATOMS AND BEING SELECTED FROM THE CLASS CONSISTING OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED HYDROXY CARBOXYLIC ACIDS, UNSUBSTITUTED ACYLATED HYDROXY CARBOXYLIC ACIDS, LOWER ALKANOL ESTERS OF UNSUBSTITUTED CARBOXYLIC ACIDS, GLYCERIDES OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED CARBOXYLIC ACID CHLORIDES AND UNSUBSTITUTED CARBOXYLIC ACID ANHYDRIDES, AND THE OXALKYLATION AGENT BEING SELECTED FROM THE CLASS CONSISTING OF ALPHA-BETA ALKYLENE OXIDES AND STYRENE OXIDE. 